This invention relates to novel suspension mediums and stable liquid suspension compositions formed with same which can be used in a water-based fluid.
Water-based fluids such as, for example, drilling fluids and mining fluids, are useful in a variety of industrial applications. It is well known to those skilled in the art of drilling wells to tap subterranean deposits of natural resources such as gas, geothermal steam or oil, especially when drilling by the rotary method or the percussion method wherein cuttings must be removed from the bore hole, that it is necessary to use a drilling fluid.
The use of water-based fluids in workover and completion fluids in oil field operations is also well known. Workover fluids are those fluids used during remedial work in a drilled well. Completion fluids are those fluids used during drilling and during the steps of completion of the well.
Additives, chemicals, or other materials are often added to such water-based fluids for various reasons such as for controlling water loss, increasing viscosity, reducing corrosion, altering pH, and increasing density of the fluids. However, the addition of such materials to water-based fluids can be difficult unless proper precautions are taken to preclude agglomeration or plugging.
Liquid additives and processes therefor have been developed to overcome some of the problems. For example, U.S. Pat. No. 5,091,448 provides an excellent stable liquid additive and process for preparing the stable liquid additive suspension. However, such stable liquid additive suspension contains a hydrocarbon as a liquid carrier which precludes the use of such systems in some areas where environmental regulations are of concern.
It is therefore highly desirable to develop a liquid suspension composition which remains stable and is useable as an additive in water or water-based fluids and which is environmentally friendly for use in oil field applications.
It is thus an object of this invention to provide a stable liquid suspension composition which is environmentally friendly and useful in oil field applications.
Another object of this invention is to provide a novel suspending agent which is useful for the formation of stable suspension compositions.
Other aspects, objects, and the several advantages of the invention will become more apparent in light of the following disclosure.
The present invention is based upon our discovery that a stable suspension composition which is environmentally friendly and thus readily useful in oil field applications is obtained when there is employed as the suspension medium a composition which is formed by the admixing of a liquid carrier, a liquid carrier soluble resin, an organophyllic clay, and an activator. Such suspension compositions exhibit excellent shelf life and avoid the use of a hydrocarbon which would otherwise preclude the use of such suspension compositions where environmental regulations are of concern.
The ingredients useful in preparing the novel suspension mediums in accordance with the present invention comprise a liquid carrier, a liquid carrier soluble resin, an activator, and an organophyllic clay.
The term xe2x80x9cliquid carrierxe2x80x9d as used herein is intended to mean a compound of the formula 
wherein R1 is a C10-C20 alkyl, preferably C15-C18, and more preferably C17, and R2 is a lower alkyl radical of 1 to 10 carbon atoms, preferably 8. In a presently preferred embodiment of the invention, the liquid carrier is the 2-ethylhexyl oleate (Finagreed BDMF ester from Fina Chemicals).
The term xe2x80x9cliquid carrier soluble resinxe2x80x9d as used herein is intended to mean any resin which is soluble in the liquid carrier component of the suspension medium. Examples of such soluble resins include styrene isoprene copolymers, styrene ethylene-propylene block copolymers, styrene isobutylene copolymers, styrene butadiene copolymers, polybutylene, polystyrene, polyethylene-propylene copolymers, methyl methacrylate, and mixtures thereof.
Presently preferred are block copolymers, examples of which include, but are not limited to, styrene ethylene-propylene block copolymer, hydrogenated styrene-isoprene block copolymer, and styrene butadiene copolymer. Most particularly preferred are hydrogenated styrene-isoprene block copolymers, examples of which include, but are not limited to, compounds sold under the trademark SHELLVIS 40 and SHELLVIS 50 by Shell Chemical Company.
The term xe2x80x9corganophyllic clayxe2x80x9d as employed herein is intended to mean those clays which have been treated with a cationic surfactant so as to distribute amine groups on the surface of some. Examples of such clays include kaolinite, halloysite, vermiculite, chlorite, attapulgite, smectite, montmorillonite, illite, bentonite, hectorite, and mixtures thereof. The presently preferred clay is sodium montmorillonite, which is also known as hectorite clay, which has been treated with an alkylaryl amine surfactant. Such organophyllic clays are commercially available from Rheox, Inc. of Hightstown, N.J.
The term xe2x80x9cactivatorxe2x80x9d as used herein is intended to mean a compound which is added to the suspension medium to assist the clay component therein to develop viscosity. Such compounds are at least one selected from the group consisting of lower alkyl alcohols of the formula ROH wherein R is a 1 to 8 carbon alkyl, preferably 2, a glycol such as ethylene glycol and propylene glycol and glycerine.
The term xe2x80x9csolid particulatexe2x80x9d as employed herein is intended to mean any solid particle which is capable of being suspended in the novel suspension medium of the present invention. Any solid particulate that is substantially insoluble, or partially soluble in the liquid suspending medium can be used in the practice of this invention. Examples of suitable solid particulates include, but are not limited to polymers, herbicides, insecticides, sulfonated asphalt, salts of sulfonated asphalt, lime, sodium bicarbonate, sodium carbonate, molybdenum disulfide, sodium hydroxide, graphite, zinc, tin, quebracho, lignin, lignosulfonate, lignite, caustisized lignate, lignosulfoante, chrome lignosulfoante, naphthalenesulfonate, unintahite (gilsonite), and combinations of two or more of same.
In one presently preferred embodiment of the present invention, the solid particulate is at least one compound selected from the group consisting of guar gum, cellulose derivatives such as carboxy ethyl cellulose and carboxyl methyl cellulose, xanthan gum, sodium tetra borate (Borax), ethylene diamine tetracetic acid, nitrillotetraacetic acid, polyacrylamide, and vinyl polymers.
Blending of the selected ingredients for forming the suspension medium of the present invention can be carried out in any manner but generally the selected ingredients are added to the liquid carrier. It is preferred that following the addition of the clay component to the liquid carrier there is thereafter added the activator at a high shear rate to permit the clay or silica component to develop viscosity and thereafter the selected liquid carrier soluble resin is added to form the suspension medium to which the solid particulate is then added with agitation so as to form the desired stable particulate suspension of this invention.
The solid particulates employed in the formation of the stable suspensions of the present invention should in general be a particle size such that the diameter of same in the range of from about 1 to about 2500 microns.
All water soluble polymers are useful in the practice of this invention. Examples of such polymers and the methods for producing and/or obtaining them are disclosed in Bishop, U.S. Pat. No. 4,735,659, which is incorporated herein by reference. Particularly preferred is carboxy methyl cellulose. The water soluble polymers are well known in the art. Such water soluble polymers are selected from the group consisting of the cellulose ethers, starches, gums, vinyl polymers, acrylic polymers, and bipolysaccharides. Further examples of such polymers are disclosed in Hostettler et al, U.S. Pat. No. 5,091,448, which is incorporated herein by reference. Further examples of solid particulates which can be employed in the practice of the present invention are also disclosed in Patel et al, U.S. Pat. No. 5,834,533, which is incorporated herein by reference.
In the practice of certain preferred embodiments of the present invention through the selection of the solid particulate there is achieved certain advantages when the suspension is utilized in drilling operations. Thus, when there is used a suspension comprising guar gum, or a cellulose derivative such as hydroxy ethyl cellulose or carboxy methyl cellulose, there is obtained enhanced water loss control. When there is employed a suspension composition comprising a xanthan gum, there is obtained an enhancement of the suspension capability of the drilling fluid. Thus, through the use of the suspension systems of the present invention there is obtained systems which are not only environmentally friendly but which also assist in the enhancement of drilling, fracturing, or completion fluids.
In addition to the use of the liquid carrier for the suspension medium ingredients, there can be utilized as the liquid carrier a mixture of the selected ester carrier and a vegetable oil. Such vegetable oils are triglycerides extracted from seeds. Examples of suitable vegetable oils are soybean oil, peanut oil, sunflower seed oil, and rap seed oil. Generally, when the vegetable oil is employed, such oil is employed in an amount in the range of about 10 to about 50 weight percent of the total liquid carrier.
In addition, while not required for the formation of the suspension systems of the present invention, there can be employed water in an amount in the range of from about 0.2 to about 15 weight percent of the liquid carrier when the solid particulate is a water soluble polymer. Such water has been found to dissolve in the solid particulate polymer and thus serves to reduce the density of the particulate.
The ranges of the ingredients useful in the practice of this invention are as follows:
To the resulting suspension medium there can be added the selected solid particulate in an amount in the range of about 10 to about 70 weight percent, preferably about 30 to about 60 weight percent, based on the weight of the total composition.
The addition of an antioxidant, a surfactant, a biocide to the basic suspension composition can be exercised, if desired, in the practice of this invention.
The product of this invention normally has a gel strength that is capable of suspending particulate matter. Additionally, this gel strength develops very rapidly or almost immediately. In addition, the suspensions have a desirable fragile property which is evidenced by the ease with which it pours.
The product of this invention is primarily tested by observation for stability over a wide temperature range. Stability can be measured by means of a rule or other such graduated device whereby there is determined the thickness from the interface of the clear liquid portion of that portion of liquid that separates from the portion of liquid containing suspended solids.